Acrylic Grafted Polyether Resins Based on Phenol Steric Acid and Coating Compositions Formed Therefrom

ABSTRACT

Coating compositions can be prepared from an acrylic grafted polyether resin, wherein the smallest difunctional hydroxyl phenyl segment used to form the acrylic grafted polyether resin has a molecular weight greater than about 500, and wherein the smallest difunctional hydroxyl phenyl segment used to form the acrylic grafted polyether resin does not comprise two or more non-impaired hydroxyl groups attached to two or more different five-membered or six-membered carbon atom rings in a segment having a molecular weight less than about 500. The acrylic grafted polyether resin can be prepared by reacting a dihydroxyl compound and/or a diamine compound with a phenol stearic acid compound to produce a diphenol, reacting the diphenol with a diglycidyl ether compound to form a polyether resin, and mixing the polyether resin with an ethylenically unsaturated monomer component in the presence of an initiator to form the acrylic grafted polyether resin.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to acrylic grafted bisphenol-A freepolyether resins based on phenol stearic acid, coating compositionshaving the acrylic grafted polyether resins, methods of coatingsubstrates with the coating compositions, and substrates coated with thecoating compositions.

2. Description of Related Art

Many coating compositions currently used in the packaging coatingsindustry do not cure well when blended with phenolic resin crosslinkers.Melamine and benzoguanamine have been used as co-crosslinkers withphenolic resins to crosslink polyesters and cure has improved, but it isdesired in the packaging coatings industry to avoid triazines, such asmelamine and benzoguanamine, for health reasons. Isocyanates have beenused as crosslinkers for polyesters, but the resulting coatingcompositions have less corrosion resistance compared to coatingcompositions crosslinked with phenolic crosslinkers, plus it is desiredin the packaging coatings industry to avoid using isocyanates for healthreasons. Phenol-terminated polyesters have been crosslinked withmelamine crosslinkers, but melamine is undesirable for health reasons asmentioned above. Polyesters have also been terminated withp-hydroxybenzoic acid, but it is also desired in the packaging coatingsindustry to avoid hydroxybenzoic acids, as parabens are materials ofhigh concern. Polyesters formed from the reaction product of polyols andbis-epoxies reacted with phenolic carboxylic acids/esters are also used,but carboxylic phenols are also undesired in the packaging coatingsindustry for health reasons. Polyesters have also been terminated withphenols from cardanol, a known sensitizer, but this is also a materialof concern.

There is a desire among some consumers and brand owners in the packagingcoatings industry to have coating compositions which are also free, orsubstantially free, of bisphenol A and polyvinyl chloride and which donot suffer from the above drawbacks.

SUMMARY OF THE INVENTION

The present invention relates to acrylic grafted bisphenol-A freeacrylic grafted polyether resins based on phenol stearic acid, coatingcompositions having the acrylic grafted polyether resins, methods ofcoating substrates with the coating compositions, and substrates coatedwith the coating compositions. As used herein, the term “phenol stearicacid compound” is a compound prepared from the reaction product of oleicacid and a phenol, wherein the primary reaction product is10-(p-hydroxyphenyl)-octadecanoic acid (also known as9(10)-(hydroxyphenyl) octadecanoic acid), and wherein other materialsformed from the reaction of oleic acid and phenol may be present in thereaction product.

In some embodiments of the invention, the smallest difunctional hydroxylphenyl segment used to form the acrylic grafted polyether resin has amolecular weight greater than about 500, and the smallest difunctionalhydroxyl phenyl segment used to form the acrylic grafted polyether resindoes not comprise two or more non-impaired hydroxyl groups attached totwo or more different five-membered or six-membered carbon atom rings ina segment having a molecular weight less than about 500. Thesestructures with molecular weights less than about 500 and/or whichcomprise two or more non-impaired hydroxyl groups attached to two ormore different five-membered or six-membered carbon atom rings in asegment having a molecular weight less than about 500 are suspected tobe endocrine disruptors and thus undesirable for use in coatingcompositions which contact food or beverages. Monomers or the smallestdifunctional hydroxyl phenyl segments used to form acrylic graftedpolyether resins having a molecular weight greater than about 500 and/ornot comprising two or more non-impaired hydroxyl groups attached to twoor more different five-membered or six-membered carbon atom rings in asegment having a molecular weight less than about 500 are not suspectedto be endocrine disruptors and are thus desirable for use in coatingcompositions which contact food or beverages.

In certain embodiments, an acrylic grafted polyether resin can beprepared by a method comprising reacting a dihydroxyl compound and/or adiamine compound with a phenol stearic acid compound to produce adiphenol, reacting the diphenol with a diglycidyl ether compound to forma polyether resin, and mixing the acrylic grafted polyether resin withan ethylenically unsaturated monomer component in the presence of aninitiator to form the acrylic grafted polyether resin. The acrylicgrafted polyether resins can crosslink with phenolic resins to producecoating compositions. The acrylic grafted polyether resins can be usedto form coating compositions having excellent flexibility, hardness andresistance to attack by foods and beverages.

In some embodiments, the present invention includes methods of coating asubstrate by applying the coating composition to the substrate.Substrates coated with the coating compositions are also disclosed. Insome embodiments, the substrate is a can or packaging.

DETAILED DESCRIPTION OF THE INVENTION

As used in the afore-discussed embodiments and other embodiments of thedisclosure and claims described herein, the following terms generallyhave the meaning as indicated, but these meanings are not meant to limitthe scope of the invention if the benefit of the invention is achievedby inferring a broader meaning to the following terms.

The present invention includes substrates coated at least in part with acoating composition of the invention and methods for coating thesubstrates. The term “substrate” as used herein includes, withoutlimitation, cans, metal cans, easy-open-ends, packaging, containers,receptacles, or any portions thereof used to hold, touch or contact anytype of food or beverage. Also, the terms “substrate”, “food can(s)”,“food containers” and the like include, for non-limiting example, “canends”, which can be stamped from can end stock and used in the packagingof food and beverages.

The present invention relates to acrylic grafted bisphenol-A freepolyether resins based on phenol stearic acid, coating compositionshaving the acrylic grafted polyether resins, methods of coatingsubstrates with the coating compositions, and substrates coated with thecoating compositions.

In some embodiments of the invention, the smallest difunctional hydroxylphenyl segment used to form the acrylic grafted polyether resin has amolecular weight greater than about 500, and the smallest difunctionalhydroxyl phenyl segment used to form the acrylic grafted polyether resindoes not comprise two or more non-impaired hydroxyl groups attached totwo or more different five-membered or six-membered carbon atom rings ina segment having a molecular weight less than about 500. Thesestructures with molecular weights less than about 500 and/or whichcomprise two or more non-impaired hydroxyl groups attached to two ormore different five-membered or six-membered carbon atom rings in asegment having a molecular weight less than about 500 are suspected tobe endocrine disruptors and thus undesirable for use in coatingcompositions which contact food or beverages. Monomers or the smallestdifunctional hydroxyl phenyl segments used to form acrylic graftedpolyether resins having a molecular weight greater than about 500 and/ornot comprising two or more non-impaired hydroxyl groups attached to twoor more different five-membered or six-membered carbon atom rings in asegment having a molecular weight less than about 500 are not suspectedto be endocrine disruptors and are thus desirable for use in coatingcompositions which contact food or beverages.

In certain embodiments, the acrylic grafted polyether resin can beprepared by a method comprising reacting a dihydroxyl compound and/or adiamine compound with a phenol stearic acid compound to produce adiphenol, reacting the diphenol with a diglycidyl ether compound to forma polyether resin, and mixing the polyether resin with an ethylenicallyunsaturated monomer component in the presence of an initiator to formthe acrylic grafted polyether resin. The acrylic grafted polyetherresins can be used to form coating compositions having excellentflexibility, hardness and resistance to attack by foods and beverages.

For non-limiting example, the dihydroxyl compound may comprise1,4-cyclohexane dimethanol, butane diol, neopentyl glycol,1,3-cyclohexane dimethanol, ethylene glycol, propylene glycol,1,3-propane diol, trimethylol propane, diethylene glycol, a polyetherglycol, benzyl alcohol, 2-ethyl hexanol, a polyester, a polycarbonate, ahydroxyl functional polyolefin, or a mixture thereof, the diaminecompound may comprise a piperazine compound, ethylene diamine,hexamethylene diamine, a fatty diamine, or a mixture thereof, and thediglycidyl ether compound may comprise diglycidyl ethers of1,4-cyclohexane dimethanol, butane diol, neopentyl glycol, cyclohexanedimethanol, ethylene glycol, propylene glycol, 1,3-propane diol,trimethylol propane, diethylene glycol, a polyether glycol, benzylalcohol, 2-ethyl hexanol, a polyester, a polycarbonate, a hydroxylfunctional polyolefin, or a mixture thereof.

The phenol stearic acid compound can be present in a mole ratio of about1:1 of the hydroxyl or amine functionality. It is possible to have aslight excess of the phenol stearic acid compound, which may lead tosome ester formation when the epoxy is reacted to form the polyether, ora slight excess of hydroxyl or amine, which may lead to broaderpolydispersity of the polyether formed.

Non-functional and/or hydroxyl functional monomers may be used,optionally with higher levels of an acid functional monomers to placethe acrylic grafted polyether resin in solution. For non-limitingexample, the acrylic grafted polyether resin may be prepared from anethylenically unsaturated monomer component having non-functionalethylenically unsaturated monomers such as, for non-limiting example,butyl acrylate, methyl methacrylate, styrene, benzyl methacrylate andthe like and mixtures thereof, and optionally with lesser amounts offunctional monomers such as, for non-limiting example, hydroxy propylmethacrylate, hydroxy ethyl acrylate, glycidyl methacrylate, acrylicacid, methacrylic acid, acetoacetoxy ethyl methacrylate, phosphateesters monomethacrylate and the like and mixtures thereof. In someembodiments of the invention, the hydroxyl functional monomer is addedat a level up to about 30% by weight of the ethylenically unsaturatedmonomer component mixture, the acid functional monomer is added at alevel up to about 30% by weight of the ethylenically unsaturated monomercomponent mixture. In some embodiments, acetoacetoxy ethyl methacrylateis added at a level up to about 30% by weight of the ethylenicallyunsaturated monomer component mixture. Phosphate esters ofmonomethacrylates (such as Sipomer Pam-100, Pam-200 and Pam-400) can beadded at a level up to about 20% by weight of the ethylenicallyunsaturated monomer component mixture. In some embodiments, about 10 toabout 50% by weight of the ethylenically unsaturated monomer componentmixture is an acid functional monomer. In some embodiments, the acidfunctional monomer is methacrylic acid.

This acid monomer may be neutralized with an amine to form a saltallowing the acrylic grafted polyether resin to be dispersed in water.The neutralizer may include, without limitation, ammonia, a tertiaryamine, such as, for non-limiting example, dimethylethanolamine,2-dimethylamino-2-methyl-1-propanol, tributylamine, or a combinationthereof. For non-limiting example, the neutralizer may be employed in anamount up to about 100% based on of the amount of acid to be neutralizedin the system.

The acrylic grafted polyether resin may be prepared in the presence ofan initiator. The initiator can be added after the mixture is cooled. Insome embodiments, the initiator is added over about 2 hours. Theinitiator may include without limitation, azo compounds such as fornon-limiting example, 2,2′-azo-bis(isobutyronitrile),2,2′-azo-bis(2,4-dimethylvaleronitrile), and1-t-butyl-azocyanocyclohexane), hydroperoxides such as for non-limitingexample, t-butyl hydroperoxide and cumene hydroperoxide, peroxides suchas for non-limiting example, benzoyl peroxide, caprylyl peroxide,di-t-butyl peroxide, ethyl 3,3′-di(t-butylperoxy) butyrate, ethyl3,3′-di(t-amylperoxy) b utyrate, t-amylperoxy-2-ethyl hexanoate,1,1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoate, and t-butylperoxypivilate, peresters such as for non-limiting example, t-butylperacetate, t-butyl perphthalate, and t-butyl perbenzoate, as well aspercarbonates, such as for non-limiting example,di(1-cyano-1-methylethyl)peroxy dicarbonate, perphosphates, t-butylperoctoate, and the like and mixtures thereof. In some embodiments, theinitiator is present in an amount from about 0.1 to about 15%, andalternatively from about 1 to about 5%, based on the weight of themonomer mixture. A preferred initiator to achieve carbon-carbon graftingis benzoyl peroxide. It is also possible to pre-form the acrylicpolymer, then add it to the polyether epoxide, react the acid functionalacrylic with the epoxide and then disperse the ester grafted materialinto water.

In some embodiments, the acrylic grafted polyether resin is crosslinkedwith a phenolic crosslinker to form a curable coating composition. Theweight ratio of the phenolic crosslinker to the acrylic graftedpolyether resin may be from about 5/95 to about 40/60 at about 30-60%solids. The crosslinked coating composition may provide excellent filmperformance at very short baking for coil applications.

Optionally, the mixture of acrylic grafted polyether resin andcrosslinker can occur in the presence of a cure catalyst. Cure catalystsinclude, for non-limiting example, dodecyl benzene sulfonic acid,p-toluene sulfonic acid, phosphoric acid, and the like and mixturesthereof. In some embodiments, other polymers may be blended into thecoating composition, such as without limitation, polyethers, polyesters,polycarbonates, polyurethanes and the like, as well as mixtures thereof.Cure conditions for packaging coatings in some embodiments are about 5to about 60 seconds at about 400° F. to about 600° F., and alternativelyabout 5 seconds to about 20 seconds at about 400° F. to about 500° F.

The acrylic grafted polyether resins and the coating compositions of theinvention can include conventional additives known to those skilled inthe art, such as without limitation, flow agents, surface active agents,defoamers, anti-cratering additives, lubricants, heat-release additives,and cure catalysts.

In some embodiments of the invention, one or more acrylic graftedpolyether resins or coating compositions having the acrylic graftedpolyether resins are applied to a substrate, such as for non-limitingexample, cans, metal cans, easy-open-ends, packaging, containers,receptacles, can ends, or any portions thereof used to hold or touch anytype of food or beverage. In some embodiments, one or more coatings areapplied in addition to the coating compositions of the presentinvention, such as for non-limiting example, a prime coat may be appliedbetween the substrate and the coating composition.

The coating compositions can be applied to substrates in any mannerknown to those skilled in the art. In some embodiments, the coatingcompositions are sprayed or roll coated onto a substrate.

When applied, the coating compositions contain, for non-limitingexample, between about 20% and about 40% by weight polymeric solidsrelative to about 60% to about 80% solvent. For some applications,typically those other than spraying, solvent borne polymeric solutionscan contain, for non-limiting example, between about 20% and about 60%by weight polymer solids. Organic solvents are utilized in someembodiments to facilitate roll coating or other application methods andsuch solvents can include, without limitation, n-butanol,2-butoxy-ethanol-1, xylene, propylene glycol, N-butyl cellosolve,diethylene glycol monoethyl ether and other aromatic solvents and estersolvents, and mixtures thereof. In some embodiments, N-butyl cellosolveis used in combination with propylene glycol. The resulting coatingcompositions are applied in some embodiments by conventional methodsknown in the coating industry. Thus, for non-limiting example, spraying,rolling, dipping, coil coating and flow coating application methods canbe used. In some embodiments, after application onto a substrate, thecoating composition is thermally cured at temperatures in the range ofabout 200° C. to about 250° C., and alternatively higher for timesufficient to effect complete curing as well as volatilizing anyfugitive components.

The coating compositions of the present invention can be pigmentedand/or opacified with known pigments and opacifiers in some embodiments.For many uses, including food use for non-limiting example, the pigmentcan be zinc oxide, carbon black, or titanium dioxide. The resultingcoating compositions are applied in some embodiments by conventionalmethods known in the coating industry. Thus, for non-limiting example,spraying, rolling, dipping, and flow coating application methods can beused for both clear and pigmented films. In some embodiments, afterapplication onto a substrate, the coating composition is thermally curedat temperatures in the range of about 130° C. to about 250° C., andalternatively higher for time sufficient to effect complete curing aswell as volatilizing any fugitive components.

For substrates intended as beverage containers, the coating are appliedin some embodiments at a rate in the range from about 0.5 msi to about15 milligrams per square inch of polymer coating per square inch ofexposed substrate surface. In some embodiments, the water-dispersiblecoating is applied at a thickness between about 0.1 msi and about 1.15msi.

For substrates intended as beverage easy-open-ends, the coating areapplied in some embodiments at a rate in the range from about 1.5 toabout 15 milligrams per square inch of polymer coating per square inchof exposed substrate surface. Conventional packaging coatingcompositions are applied to metal at about 232 to about 247° C. Some ofthe coating compositions of the current invention achieve good resultsat about 230° C. or below, such as at about 210° C. or below. Thisdecreased temperature provides an energy savings to the coater, and itmay allow the use of different alloys, such as tin-plated steel used foreasy-open-ends. This also allows to recycle the ends together with thecan body. When used as a coating for the easy-open-end of a metalcontainer, the coatings of the invention exhibit resistance to retortedbeverages, acidified coffees, isotonic drinks, and the like. In someembodiments, the solids content of the coating composition is greaterthan about 30% and the coating composition has a viscosity from about 35to about 200 centipoise at 30% solids or above to produce a film weightof about 6 to about 8 msi (milligrams per square inch) so that overblister is minimized and so that the film can have good chemicalresistance, such as aluminum pick-up resistance. Some of the coatingcompositions of the current invention can be used for both inside andoutside easy-open-end applications.

EXAMPLES

The invention will be further described by reference to the followingnon-limiting examples. It should be understood that variations andmodifications of these examples can be made by those skilled in the artwithout departing from the spirit and scope of the invention.

Example 1—Synthesis of a Diphenol

78 grams of 1,4-cyclohexane dimethanol, 506 grams of phenol stearic acidand 0.20 grams of butyl stanoic acid were heated with a distillationcolumn and overhead to 225° C. About 18 grams of water was produced.Xylene was used as a carrier solvent to achieve a final acid number ofless than 5 mg KOH/gram of the resin.

Example 2—Synthesis of an Acrylic Grafted Polyether Resin

155 grams of the diphenol from Example 1, 59 grams of cyclohexanedimethanol diglycidyl ether and 0.2 grams of 2-phenyl imidazole wereheated to 180° C. and held for 2 hours. The epoxy equivalent weight was2430. The mixture was held for 2 more hours at 190° C. The epoxyequivalent weight was 3930.

Example 3—Synthesis of an Acrylic Grafted Polyether Resin

70 grams of the acrylic grafted polyether resin from Example 2 and 100grams of butyl cellosolve were heated to 120° C. To the resultingmixture, 18 grams of methacrylic acid, 10 grams of butyl acrylate, 42grams of styrene and 5 grams of benzoyl peroxide were added over 2 hoursunder a nitrogen blanket. The mixture was held for 30 minutes 1 gram oft-butyl peroctoate was added and the mixture was held for 30 minutes.Another 1 gram of t-butyl peroctoate was added and the mixture was heldfor 30 minutes. The resulting mixture was cooled to 80° C. 15 grams ofdiemethylethanolamine in 20 grams of water were added, followed by anadditional 280 grams of water under shear. A stable, translucentdispersion was produced.

Example 4—Synthesis of a Coating Composition

18 grams of a phenolic resin dissolved in 18 grams of butyl cellosolvewas added to 100 grams of the acrylic grafted polyether resin fromExample 3. The resulting coating film was drawn down on ETP steel with a#7 rod and baked for 10 minutes at 200° C. An amber colored, glossy filmwas produced that had a 2H pencil hardness, was able to withstand 100MEK rubs with very slight mar, had 100% tape-off cross hatch adhesion,no cracking after 20 inch-pound reverse impacts, and no blush oradhesion loss after 1 hour in boiling water.

Example 5—Synthesis of a Diphenol

79.3 grams of 1,4-cyclohexane dimethanol, 451 grams of phenol stearicacid and 0.20 grams of butyl stanoic acid were heated under nitrogen to225° C. over 1 hour in a 1 liter flask equipped with a stiffer,thermocouple temperature controller, and a packed distillation column(10 inch Vigreux topped with 4 inches of glass tube section packing).The mixture was held until the column head temperature dropped to about60° C. The column was switched for a Dean Stark trap and xylene wasadded to obtain a steady reflux for 6 hours. The mixture was cooled andthe final acid number was 4 mg KOH/g resin.

Example 6—Synthesis of an Acrylic Grafted Polyether Resin

128 grams of the diphenol from Example 5, 40.4 grams of GE-22 (CVCIndustries) diglycidyl ether of 1,4-cyclohexane diglycidyl ether and 0.5grams of 2-phenyl imidazole were heated to 175° C. and held for 4 hours.The epoxy equivalent weight was 7140 and the viscosity was 478 poise at50° C.

Example 7—Synthesis of a Diphenol

451 grams of phenol stearic acid, 43.1 grams of piperazine and 0.20grams of butyl stanoic acid were heated under nitrogen to 225° C. over 1hour in a 1 liter flask equipped with a stirrer, thermocoupletemperature controller, and a packed distillation column (10 inchVigreux topped with 4 inches of glass tube section packing). The mixturewas held until the column head temperature dropped to about 60° C. Thecolumn was switched for a Dean Stark trap and xylene was added to obtaina steady reflux for 6 hours. The mixture was cooled and the final acidnumber was 9.3 mg KOH/g resin.

Example 8—Synthesis of a Diamide

2,256 grams of phenol stearic acid, 329 grams of Dytec A, and 0.95 gramsof butyl stanoic acid were heated to 185° C. in a glass flask. Thereaction temperature was controlled such that the head temperature on adistillation column did not exceed about 98° C. as the batch temperaturewas raised to 225° C. The batch was held at about 225° C. until the headtemperature dropped below about 70° C. Water continued to distill off(approximately 80 grams) with an overhead for two hours, then switchedto a xylene azeotrope. About 20 grams of xylene remained in the diamide.The mixture was cooked to an acid number of about 5 mg KOH/grams ofresin and a base number of less than 2.

Example 9—Synthesis of a Diester

961 grams of phenol stearic acid, 160 grams of cyclohexane dimethanol,and 0.4 grams of butyl stanoic acid were heated to 185° C. in a glassflask. The reaction temperature was controlled such that the headtemperature on a distillation column did not exceed about 98° C. as thebatch temperature was raised to 225° C. The batch was held at about 225°C. until the head temperature dropped below about 70° C. Water continuedto distill off (approximately 80 grams) with an overhead for two hours,then switched to a xylene azeotrope. About 20 grams of xylene remainedin the diester. The mixture was cooked to an acid number of about 5 mgKOH/grams of resin.

Example 10—Epoxy Advancement

800 grams of the diamide from example 8, 277 grams of cyclohexanedimethanol diglycidyl ether, and 3 grams of 2-phenyl imidazole wereheated to 175° C. in a glass flask. There was a slight exotherm to180-185° C. The mixture was held for four hours until the viscosityreached 80-110 p (100° C. cone and plate viscometer). The mixture wascooled to 120° C. and 150 grams of butyl cellosolve and 150 grams ofbutanol were added. The mixture continued to cool and was poured out atroom temperature.

Example 11—Epoxy Advancement

1,253 grams of the diamide from example 8, 352 grams of butane dioldiglycidyl ether, and 3 grams of 2-phenyl imidazole were heated to 175°C. in a glass flask. There was a slight exotherm to 180-185° C. Themixture was held for four hours until the viscosity reached 80-110 p(100° C. cone and plate viscometer). The mixture was cooled to 120° C.and 150 grams of butyl cellosolve and 150 grams of butanol were added.The mixture continued to cool and was poured out at room temperature.

Example 12—Synthesis of an Epoxy-Acrylic Grafted Emulsion

950 grams of the epoxy in example 10 were heated to 115° C. in a glassreactor. 95 grams of butyl cellosolve and 222 grams of butanol wereadded. Next, the following mixture was added over two hours: 152 gramsof methyl acrylic acid, 430 grams of styrene, 13 grams of ethylacrylate, 51 grams of benzoyl peroxide and 63 grams of butyl cellosolve.After the feed finished, the contents of the reactor were held at 155°C. for another hour. 8 grams of peroctoate were added and the mixturewas held for another hour. The mixture was cooled to 90° C. and amixture of 106 grams of dimethylethanolamine and 106 grams of water wasadded to the reactor over 15 minutes. The temperature was held at 85° C.for 30 minutes. 1714 grams of water was added and the mixture wascooled.

Example 13—Synthesis of an Epoxy-Acrylic Grafted Emulsion

700 grams of the epoxy in example 10 were heated to 115° C. in a glassreactor. 17 grams of butyl cellosolve and 84 grams of butanol wereadded. Next, the following mixture was added over two hours: 80 grams ofmethyl acrylic acid, 94 grams of styrene, 7 grams of ethyl acrylate, 27grams of benzoyl peroxide and 33 grams of butyl cellosolve. After thefeed finished, the contents of the reactor were held at 155° C. foranother hour. 8 grams of peroctoate were added and the mixture was heldfor another hour. The mixture was cooled to 90° C. and a mixture of 56grams of dimethylethanolamine and 56 grams of water was added to thereactor over 15 minutes. The temperature was held at 85° C. for 30minutes. 838 grams of water was added and the mixture was cooled.

Example 14—Synthesis of an Epoxy-Acrylic Grafted Emulsion

1,260 grams of the epoxy in example 11 were heated to 115° C. in a glassreactor. 30 grams of butyl cellosolve and 150 grams of butanol wereadded. Next, the following mixture was added over two hours: 144 gramsof methyl acrylic acid, 175 grams of styrene, 12 grams of ethylacrylate, 29 grams of benzoyl peroxide and 60 grams of butyl cellosolve.After the feed finished, the contents of the reactor were held at 155°C. for another hour. 7 grams of peroctoate were added and the mixturewas held for another hour. The mixture was cooled to 90° C. and amixture of 101 grams of dimethylethanolamine and 101 grams of water wasadded to the reactor over 15 minutes. The temperature was held at 85° C.for 30 minutes. 1,931 grams of water was added and the mixture wascooled.

Example 15—Epoxy Advancement

800 grams of the diester from example 9, 277 grams of cyclohexanedimethanol diglycidyl ether, and 3 grams of 2-phenyl imidazole wereheated to 175° C. in a glass flask. There was a slight exotherm to180-185° C. The mixture was held for four hours until the viscosityreached 80-110 p (100° C. cone and plate viscometer). The mixture wascooled to 120° C. and 150 grams of butyl cellosolve and 150 grams ofbutanol were added. The mixture continued to cool and was poured out atroom temperature.

Example 16—Synthesis of an Epoxy-Acrylic Grafted Emulsion

1,260 grams of the epoxy in example 15 were heated to 115° C. in a glassreactor. 30 grams of butyl cellosolve and 150 grams of butanol wereadded. Next, the following mixture was added over two hours: 144 gramsof methyl acrylic acid, 175 grams of styrene, 12 grams of ethylacrylate, 29 grams of benzoyl peroxide and 60 grams of butyl cellosolve.After the feed finished, the contents of the reactor were held at 155°C. for another hour. 7 grams of peroctoate were added and the mixturewas held for another hour. The mixture was cooled to 90° C. and amixture of 101 grams of dimethylethanolamine and 101 grams of water wasadded to the reactor over 15 minutes. The temperature was held at 85° C.for 30 minutes. 1,931 grams of water was added and the mixture wascooled.

Example 17: Synthesis of a Blend Formulation

50:50 (ratio of phenyl stearate diamide-epoxy to acrylic graft) of thecyclohexane dimethanol diglycidyl ether epoxy diamide from example 12was crosslinked with a hydroxyalkamide (Primid XL-552) at 5% by weight.The blend formulation has excellent corrosion resistance after a 90minute soak at 250° F. in a 2% brine solution. The blush was marginalfor the blend after a 90 minute soak at 250° F. in a 1% lactic acidsolution. Compared to a commercial epoxy bisphenol A coating, theoverall performance was improved.

Example 18: Synthesis of a Blend Formulation

70:30 (ratio of phenyl stearate diamide-epoxy to acrylic graft) of thecyclohexane dimethanol diglycidyl ether epoxy diamide from example 13was crosslinked with a phenyl methyl silicone emulsion at 4% by weight.The blend formulation has excellent corrosion resistance after a 90minute soak at 250° F. in a 2% brine solution. The blush was better thanexample 17.

Example 19: Synthesis of a Blend Formulation

70:30 (ratio of phenyl stearate diamide-epoxy to acrylic graft) of thebutane diol diglycidyl ether epoxy diamide from example 14 wascrosslinked with a phenyl methyl silicone emulsion at 4% by weight. Theblend formulation has excellent corrosion resistance and blushresistance.

Example 20: Synthesis of a Blend Formulation

70:30 (ratio of phenyl stearate diamide-epoxy to acrylic graft) of thebutane diol diglycidyl ether epoxy diamide from example 16 wascrosslinked with a phenyl methyl silicone emulsion at 4% by weight. Theblend formulation had poor corrosion resistance and blush resistance.

What is claimed is:
 1. An acrylic grafted polyether resin, wherein thesmallest difunctional hydroxyl phenyl segment used to form the acrylicgrafted polyether resin has a molecular weight greater than about 500,and wherein the smallest difunctional hydroxyl phenyl segment used toform the acrylic grafted polyether resin does not comprise two or morenon-impaired hydroxyl groups attached to two or more differentfive-membered or six-membered carbon atom rings in a segment having amolecular weight less than about
 500. 2. The acrylic grafted polyetherresin of claim 1, wherein the acrylic grafted polyether resin isprepared by a method comprising a) reacting a dihydroxyl compound and/ora diamine compound with a phenol stearic acid compound to produce adiphenol; b) reacting the diphenol with a diglycidyl ether compound toform a polyether resin; and c) mixing the polyether resin with anethylenically unsaturated monomer component in the presence of aninitiator to form the acrylic grafted polyether resin.
 3. The acrylicgrafted polyether resin of claim 2, wherein the phenol stearic acidcompound comprises 10-(p-hydroxyphenyl)-octadecanoic acid.
 4. Theacrylic grafted polyether resin of claim 1, wherein the acrylic graftedpolyether resin is neutralized in the presence of water to form acoating composition.
 5. The acrylic grafted polyether resin of claim 2,wherein the reaction mixture comprises a crosslinker.
 6. The acrylicgrafted polyether resin of claim 5, wherein the crosslinker comprises aphenolic resin.
 7. The acrylic grafted polyether resin of claim 2,wherein the dihydroxyl compound comprises 1,4-cyclohexane dimethanol,butane diol, neopentyl glycol, 1,3-cyclohexane dimethanol, ethyleneglycol, propylene glycol, 1,3-propane diol, trimethylol propane,diethylene glycol, a polyether glycol, benzyl alcohol, 2-ethyl hexanol,a polyester, a polycarbonate, a hydroxyl functional polyolefin, or amixture thereof.
 8. The polyether resin of claim 2, wherein the diaminecompound comprises a piperazine compound, ethylene diamine,hexamethylene diamine, a fatty diamine, or a mixture thereof.
 9. Thepolyether resin of claim 2, wherein the diglycidyl ether compoundcomprises the diglycidyl ether of, 4-cyclohexane dimethanol, butanediol, neopentyl glycol, cyclohexane dimethanol, ethylene glycol,propylene glycol, 1,3-propane diol, trimethylol propane, diethyleneglycol, a polyether glycol, or a mixture thereof.
 10. The polyetherresin of claim 1, wherein the acid number of the acrylic graftedpolyether resin is less than about 30 mg KOH/resin.
 11. The acrylicgrafted polyether resin of claim 1, wherein the acrylic graftedpolyether resin is prepared in the presence of a catalyst.
 12. Theacrylic grafted polyether resin of claim 11, wherein the catalyst is anacid catalyst.
 13. The acrylic grafted polyether resin of claim 2,wherein the phenol stearic acid compound is present in a mole ratio ofabout 1:1 of the hydroxyl or amine functionality.
 14. The acrylicgrafted polyether resin of claim 1, wherein the polyether resin isprepared in the presence of an initiator comprising t-butyl peroxybenzoate, t-butyl peroctoate, dibenzoyl peroxide,1,1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoate, or a mixture thereof.15. A coating composition comprising the acrylic grafted polyether resinof claim
 1. 16. A method of coating a substrate comprising applying thecoating composition of claim 15 to the substrate.